Moisture resistant polyimide compositions

ABSTRACT

The invention relates to a moisture resistant composition comprising: a) from 20 to 80 weight percent based on the total weight of the composition of a polyetherimide copolymer made from a monomer mixture comprising 3,3′ bisphenol-A dianhydride (BPADA), and 4,4′-diaminodiphenyl sulfone (DDS); b) from 5 to 75 weight percent based on the total weight of the composition of polyetheretherketone (PEEK); and c) from 0 to 30 weight percent based on the total weight of the composition of a filler. The invention relates to a reflector substrate comprising a moisture resistant layer metalized with a reflective layer, wherein the moisture resistant layer comprising the moisture resistant composition. The invention relates to a method for producing a metalized coating without a primer comprising applying a reflective layer directly to a moisture resistant layer in the absence of a primer, wherein the moisture resistant layer comprises the moisture resistant composition.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates generally to moisture resistant compositions andin particular to moisture resistant compositions comprising a polyimidecopolymer.

2. Background

There is a continuing need for polymers having good manufacturing andperformance properties at elevated temperatures. Certain manufacturingproperties at elevated temperatures are particularly needed, forexample: metalizability, dimensional stability, and resistance towarpage. Likewise, certain performance properties are particularlyneeded, for example: moisture resistance.

Lighting reflectors, especially for automotive applications, requirematerials that can withstand the high heat produced by light sources,that have excellent dimensional stability to focus the light in a tightpattern at long distances, and that can be easily processed into complexshapes. These reflectors are usually coated with a metal, such asaluminum, to provide a highly reflective surface. To achieve this highdegree of reflectivity with low haze, a very smooth pre-coated surfaceis required. In order to achieve consistently such a smooth pre-coatedsurface, it has typically been necessary to base coat the moldedreflector with a primer prior to coating the reflector with metal.Direct metalization of molded parts is also challenging because itintroduces the additional requirements of good adhesion of the metal tothe molded part and a very smooth surface of the part as molded.

In electronic components there has been a move to leadless solder atleast partially because of the deleterious effects caused by lead on theenvironment. Replacement solders have higher melting points than leadbased solders and so polymers capable of withstanding the additionalheat necessary to melt the lead replacement solders are needed for useas, for example, substrates or coatings in close proximity to solderingpoints. Even uses such as polymer parts feeling the heat from jet enginewash, lead a continuing demand for polymers having higher heatproperties than those currently on the market.

Several classes of high heat polymers are known in the art.Polyetherimide resins are known for high heat distortion temperaturesand high glass transition temperatures that make their use as coatings,molded articles, composites, and the like very attractive where hightemperature resistance is desired. Due to their high glass transitiontemperature and high melt viscosity, however, polyetherimides can bedifficult to process into finished products. Additionally, improvementsare needed in the moisture resistance and metalizability of compositionscomprising polyetherimide resins for leadless solderable articles.

For the foregoing reasons, there is a need for metalizable, moistureresistant compositions useful for lead free solderable articles. Thereis also a need for a method of producing a metalized coating without aprimer.

BRIEF SUMMARY OF THE INVENTION

It has been surprisingly discovered that by using a specific combinationof a polyimide and a polyetheretherketone, it is possible to make acomposition that is metalizable and moisture resistant. Preferably, thecompositions according to the present invention can be made intoarticles/parts containing a metalized coating without a primer. Thecompositions according to the present invention preferably can be usedin articles that include light emitting diodes as well as otherarticles.

A first embodiment of the present invention relates to a moistureresistant composition comprising: a) from 20 to 80 weight percent basedon the total weight of the composition of a polyetherimide copolymermade from a monomer mixture comprising 3,3′ bisphenol-A dianhydride(BPADA), and 4,4′-diaminodiphenyl sulfone (DDS); b) from 5 to 75 weightpercent based on the total weight of the composition ofpolyetheretherketone (PEEK); and c) from 0 to 30 weight percent based onthe total weight of the composition of a filler.

A second embodiment of the invention relates to a reflector substratecomprising a moisture resistant layer metalized with a reflective layer,wherein the moisture resistant layer comprises: a) from 20 to 80 weightpercent based on the total weight of the composition of a polyetherimidecopolymer made from a monomer mixture comprising 3,3′ bisphenol-Adianhydride (BPADA), and 4,4′-diaminodiphenyl sulfone (DDS); b) from 5to 75 weight percent based on the total weight of the composition ofpolyetheretherketone (PEEK); and c) from 0 to 30 weight percent based onthe total weight of the composition of a filler. Preferably, thereflective layer is selected from the group consisting of silver,aluminum, and combinations thereof.

A third embodiment of the invention relates to a method for producing ametalized coating without a primer comprising applying a reflectivelayer directly to a moisture resistant layer in the absence of a primer,wherein the moisture resistant layer comprises: a) from 20 to 80 weightpercent based on the total weight of the composition of a polyetherimidecopolymer made from a monomer mixture comprising 3,3′ bisphenol-Adianhydride (BPADA), and 4,4′-diaminodiphenyl sulfone (DDS); b) from 5to 75 weight percent based on the total weight of the composition ofpolyetheretherketone (PEEK); and c) from 0 to 30 weight percent based onthe total weight of the composition of a filler. Preferably, the methodfurther comprises drying the moisture resistant layer prior to applyingthe reflective layer. Preferably, the reflective layer is applied byelectroplating or vapor-deposition.

These and other features, aspects, and advantages of the presentinvention will become better understood with reference to the followingdescription and appended claims.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to thefollowing detailed description of preferred embodiments of the inventionas well as to the examples included therein. In the following detaileddescription and in the claims, which follow, reference will be made to anumber of terms, which shall be defined to have the following meanings:

The term “reflector” refers to a light modifying device having asurface, which redirects incident light back into the medium from whichit came. Reflectors are more commonly opaque but may be transparent.Light incident on the redirecting surface of a transparent reflector mayarrive from the transparent material of the reflector itself in whichcase it is redirected back into the transparent material of thereflector, or it may arrive at the redirecting surface from some othermaterial (e.g., air) in which case it is redirected back into the othermaterial.

For purposes of the present invention a “metalized” surface is a surfacethat is covered with a coating comprising one or more metals.

For purposes of the present invention, an L.E.D. is a light emittingdiode, as that term is known to one of ordinary skill in the art.

“High Tg” refers to polymers having glass transition temperature(s) of180° C. or above.

“Popcorning” refers to an effect occurring when residual moisture,collected after conditioning, converts to steam within a component,part, surface, composition, material, or composition, to disrupt adimension thereof.

“Warpage” refers to a dimensional distortion in an object, particularlyin a molded object.

“Primer” refers to a first coating applied to a surface to reduceabsorbency and/or to improve adhesion of subsequent coatings.

For purposes of the present invention the term “coating” means a film orthin layer applied to a base material, called the substrate. In thepresent invention the substrate is made up of one or more polymers,co-polymers, and/or compositions of polymers. The coating can compriseany material which the skilled artisan would employ as a coating on apolymeric substrate, including, but not limited to, one or more metals,one or more adhesives, one or more paints, one or more alloys, one ormore solid-liquid suspensions, one or more polymers with at least one ofthe polymers in the coating having a different composition than thepolymeric substrate.

For purposes of the present invention, there can be as many layers ofcoatings on the substrate as necessary to accomplish the intendedpurpose of the article of manufacture. The term “thin” as used above,means that the thickness of the coating on the article, at the coatingsthickest point, is less than the greatest length of a straight linepassing through the center of gravity of the article and which extendsto, but not beyond the outer most boundaries of the article.

The coating may be applied by any coating means known to the skilledartisan. For example, the coating may be applied by electrolysis, vapordeposition, vacuum evaporation, sputtering, or mechanical means such asbrushing spraying, calendaring, overmolding, lamination, and rollercoating.

All numeric values are herein assumed to be modified by the term“about,” whether or not explicitly indicated. The term “about” generallyrefers to a range of numbers that one of skill in the art would considerequivalent to the recited value (i.e., having the same, function orresult). In many instances, the term “about” may include numbers thatare rounded to the nearest significant figure. Unless otherwiseindicated all parts or percentages are parts by weight or percentages byweight. Unless otherwise indicated all molecular weights are weightaverage molecular weights.

Various moisture resistant compositions according present inventionsatisfy the need for an improvement in the moisture resistance andmetalizability of polyetherimide (PEI) systems for lead free solderablearticles. Particularly preferred embodiments of the present inventionrelate to a two-phase blend of a polyimide resin, having a high glasstransition temperature (Tg) and a semi-crystalline or liquid crystalpolymer (LCP) resin. The two-phase blend is particularly useful forlight emitting diode (LED) reflector substrates. The moisture resistantcompositions according to the present invention are also preferably usedin many different electronic components. The moisture resistantcompositions according to the present invention are preferably moldedinto articles and used in the construction of semiconductor packages andother electronic devices that are exposed to lead-free solderingtemperatures.

The moisture resistant compositions according to the present arepreferably have a smooth surface and survive lead free solderingtemperatures after exposure to highly humid environments. The moistureresistant compositions according to the present invention preferablydemonstrate good metalizability; can preferably withstand exposure tohighly humid environments; and preferably exhibit good dimensionalstability by retaining molded or otherwise formed dimensions uponexposure to lead free solder reflow temperatures. Particularly preferredmoisture resistant compositions according to the present invention canbe metalized with a smooth, highly reflective surface and surviveexposure to temperatures greater than or equal to 240° C., morepreferably greater than or equal to 250° C., more preferably greaterthan or equal to 260° C., more preferably greater than or equal to 270°C., and more preferably greater than or equal to 280° C.

A first embodiment of the present invention relates to a moistureresistant composition comprising: a) from 20 to 80 weight percent basedon the total weight of the composition of a polyetherimide copolymermade from a monomer mixture comprising 3,3′ bisphenol-A dianhydride(BPADA), and 4,4′-diaminodiphenyl sulfone (DDS); b) from 5 to 75 weightpercent based on the total weight of the composition ofpolyetheretherketone (PEEK); and c) from 0 to 30 weight percent based onthe total weight of the composition of a filler. Preferably, the monomermixture further comprises 3-chlorophthalic anhydride.

Preferably, the moisture resistant composition comprises about 80 weightpercent based on the total weight of the composition of component a),about 20 weight percent based on the total weight of the composition ofcomponent b), and about 0 weight percent based on the total weight ofthe composition of component c). Preferably, the moisture resistantcomposition comprises about 70 weight percent based on the total weightof the composition of component a), about 30 weight percent based on thetotal weight of the composition of component b), and about 0 weightpercent based on the total weight of the composition of component c).Preferably, the moisture resistant composition comprises about 75 weightpercent based on the total weight of the composition of component a),about 15 weight percent based on the total weight of the composition ofcomponent b), and about 10 weight percent based on the total weight ofthe composition of component c). Preferably, the moisture resistantcomposition comprises about 65 weight percent based on the total weightof the composition of component a), about 15 weight percent based on thetotal weight of the composition of component b), and about 20 weightpercent based on the total weight of the composition of component c).Preferably, the moisture resistant composition comprises about 25 weightpercent based on the total weight of the composition of component a),about 66 weight percent based on the total weight of the composition ofcomponent b), and about 9 weight percent based on the total weight ofthe composition of component c).

Preferably, a molded part comprising the moisture resistant compositionand having a thickness of from 1 to 3 mm does not exhibit popcorning ina dry atmosphere at 260° C. More preferably, a molded part comprisingthe moisture resistant composition and having a thickness of from 1 to 3mm does not exhibit popcorning at 60° C./60% relative humidity at 260°C. Still more preferably, a molded part comprising the moistureresistant composition and having a thickness of from 1 to 3 mm does notexhibit popcorning at 80° C./85% relative humidity at 260° C.

Preferably, a molded part comprising the moisture resistant compositionand having a thickness of from 1 to 3 mm exhibits a warpage of less thanor equal to 0.5 mm in a dry atmosphere at 260° C. More preferably, amolded part comprising the moisture resistant composition and having athickness of from 1 to 3 mm exhibits a warpage of less than or equal to0.5 mm at 30° C./60% relative humidity at 260° C. Still more preferably,a molded part comprising the moisture resistant composition and having athickness of from 1 to 3 mm exhibits a warpage of less than or equal to0.5 mm at 60° C./60% relative humidity at 260° C. Particularlypreferably, a molded part comprising the moisture resistant compositionand having a thickness of from 1 to 3 mm exhibits a warpage of less thanor equal to 0.5 mm at 80° C./85% relative humidity at 260° C.

A second embodiment of the invention relates to a reflector substratecomprising a moisture resistant layer metalized with a reflective layer,wherein the moisture resistant layer comprises: a) from 20 to 80 weightpercent based on the total weight of the composition of a polyetherimidecopolymer made from a monomer mixture comprising 3,3′ bisphenol-Adianhydride (BPADA), and 4,4′-diaminodiphenyl sulfone (DDS); b) from 5to 75 weight percent based on the total weight of the composition ofpolyetheretherketone (PEEK); and c) from 0 to 30 weight percent based onthe total weight of, the composition of a filler. Preferably, thereflective layer is selected from the group consisting of silver,aluminum, and combinations thereof.

A third embodiment of the invention relates to a method for producing ametalized coating without a primer comprising applying a reflectivelayer directly to a moisture resistant layer in the absence of a primer,wherein the moisture resistant layer comprises: a) from 20 to 80 weightpercent based on the total weight of the composition of a polyetherimidecopolymer made from a monomer mixture comprising 3,3′ bisphenol-Adianhydride (BPADA), and 4,4′-diaminodiphenyl sulfone (DDS); b) from 5to 75 weight percent based on the total weight of the composition ofpolyetheretherketone (PEEK); and c) from 0 to 30 weight percent based onthe total weight of the composition of a filler. Preferably, the methodfurther comprises drying the moisture resistant layer prior to applyingthe reflective layer. Preferably, the reflective layer is applied byelectroplating.

In addition to the polymer components of the composition, otherbeneficial compositions may be added to produce an improved article ofmanufacture. The skilled artisan will appreciate the wide range ofingredients, such as heat stabilizers, fillers, or colorants, which canbe added to polymers to improve one or more manufacturing or performanceproperty.

In some cases a metal oxide may be added to the polymers of the presentinvention. In some instances the metal oxide may further improve flameresistance (FR) performance by decreasing heat release and increasingthe time to peak heat release. Titanium dioxide is of note. Other metaloxides include zinc oxides, boron oxides, antimony oxides, iron oxides,and transition metal oxides. Metal oxides that are white may be desiredin some instances. Metal oxides may be used alone or in combination withother metal oxides. Metal oxides may be used in any effective amount, insome instances at from 0.01 to 20-wt % of the polymer composition.

Other useful additives include smoke suppressants such as metal boratesalts for example zinc borate, alkali metal or alkaline earth metalborate or other borate salts. Additionally other of boron containingcompounds, such as boric acid, borate esters, boron oxides or otheroxygen compounds of boron may be useful. Additionally other flameretardant additives, such as aryl phosphates and brominated aromaticcompounds, including polymers containing linkages made from brominatedaryl compounds, may be employed. Examples of halogenated aromaticcompounds are brominated phenoxy resins, halogenated polystyrenes,halogenated imides, brominated polycarbonates, brominated epoxy resins,and mixtures thereof.

Conventional flame retardant additives, for example, phosphate esters,sulfonate salts, and halogenated aromatic compounds may also beemployed. Mixtures of any or all of these flame-retardants may also beused. Examples of halogenated aromatic compounds are brominated phenoxyresins, halogenated polystyrenes, halogenated imides, brominatedpolycarbonates, brominated epoxy resins, and mixtures thereof. Examplesof sulfonate salts are potassium perfluoro butyl sulfonate, sodiumtosylate, sodium benzene sulfonate, sodium dichloro benzene sulfonate,potassium diphenyl sulfone sulfonate and sodium methane sulfonate. Insome instances sulfonate salts of alkaline and alkaline earth metals arepreferred. Examples of phosphate flame retardants are tri arylphosphates, tri cresyl phosphate, triphenyl phosphate, bisphenol Aphenyl diphosphates, resorcinol phenyl diphosphates,phenyl-bis-(3,5,5′-trimethylhexyl phosphate), ethyl diphenyl phosphate,bis(2-ethylhexyl)-p-tolyl phosphate, bis(2-ethylhexyl)-phenyl phosphate,tri(nonylphenyl)phosphate, phenyl methyl hydrogen phosphate,di(dodecyl)-p-tolyl phosphate, halogenated triphenyl phosphates, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolylbis(2,5,5′-trimethylhexyl) phosphate, 2-ethylhexyldiphenyl phosphate,diphenyl hydrogen phosphate, resorcinol diphosphate and the like.

In some instances it maybe desired to have flame retardant compositionsthat are essentially free of halogen atoms, especially bromine andchlorine. Essentially free of halogen atoms means that in someembodiments the composition has less than about 3% halogen by weight ofthe composition and in other embodiments less than about 1% by weight ofthe composition containing halogen atoms. The amount of halogen atomscan be determined by ordinary chemical analysis.

The composition may also optionally include a fluoropolymer in an amountof 0.01 to about 5.0% fluoropolymer by weight of the composition. Thefluoropolymer may be used in any effective amount to provide anti-dripproperties to the resin composition. Some possible examples of suitablefluoropolymers and methods for making such fluoropolymers are set forth,for example, in U.S. Pat. Nos. 3,671,487, 3,723,373 and 3,383,092.Suitable fluoropolymers include homopolymers and copolymers thatcomprise structural units derived from one or more fluorinatedalpha-olefin monomers. The term “fluorinated alpha-olefin monomer” meansan alpha-olefin monomer that includes at least one fluorine atomsubstituent. Some of the suitable fluorinated alpha-olefin monomersinclude, for example, fluoro ethylenes such as, for example, CF2=CF2,CHF═CF2, CH2=CF2 and CH2=CHF and fluoro propylenes such as, for example,CF3CF═CF2, CF3CF═CHF, CF3CH═CF2, CF3CH═CH2, CF3CF═CHF, CHF2CH═CHF andCF3CF═CH2.

Some of the suitable fluorinated alpha-olefin copolymers includecopolymers comprising structural units derived from two or morefluorinated alpha-olefin monomers such as, for example, poly(tetrafluoroethylene-hexafluoro ethylene), and copolymers comprising structuralunits derived from one or more fluorinated monomers and one or morenon-fluorinated monoethylenically unsaturated monomers that arecopolymerizable with the fluorinated monomers such as, for example,poly(tetrafluoroethylene-ethylene-propylene) copolymers. Suitablenon-fluorinated monoethylenically unsaturated monomers include forexample, alpha-olefin monomers such as, for example, ethylene,propylene, butene, acrylate monomers such as for example, methylmethacrylate, butyl acrylate, and the like, withpoly(tetrafluoroethylene) homopolymer (PTFE) preferred.

The compositions may further contain fillers (at least some of which actas reinforcements) for example fiberglass, milled glass, glass beads,flake, and the like. Minerals such as talc, wollastonite, mica, kaolinor montmorillonite clay, silica, quartz and barite may be added. Thecompositions can also be modified with effective amounts of inorganicfillers, such as, for example, carbon fibers and nanotubes, metalfibers, metal powders, conductive carbon, and other additives includingnano-scale reinforcements.

Other additives include antioxidants such as phosphites, phosphonites,and hindered phenols. Phosphorus containing stabilizers includingtriaryl phosphite and aryl phosphonates are of note as useful additives.Difunctional phosphorus containing compounds can also be employed.Stabilizers with a molecular weight of greater than or equal to about300 are preferred. In other instances phosphorus containing stabilizerswith a molecular weight of greater than or equal to 500 are useful.Phosphorus containing stabilizers are typically present in thecomposition at 0.05-0.5% by weight of the formulation. Colorants as wellas light stabilizers and UV absorbers may also be present in thecomposition. Flow aids and mold release compounds are also contemplated.Examples of mold release agents are alkyl carboxylic acid esters, forexample, pentaerythritol tetrastearate, glycerin tristearate, andethylene glycol distearate. Mold release agents are typically present inthe composition at 0.05-0.5% by weight of the formulation. Preferredmold release agents will have high molecular weight, typically greaterthan about 300, to prevent loss of the release agent from the moltenpolymer mixture during melt processing.

Polymer compositions used in articles according to the present inventionmay also include various additives such as nucleating, clarifying,stiffness and/or crystallization rate agents. These agents are used in aconventional matter and in conventional amounts.

Advantageously, it is now possible to make compositions containing aspecific combination of a polyimide and a polyetheretherketone and makea composition that is metalizable moisture resistant. It is now possibleto make compositions into articles/parts containing a metalized coatingwithout a primer.

The following examples further illustrate the present invention, inwhich all parts are by weight unless otherwise indicated.

Examples 1-58 Materials

The following neat resins were used in Examples 1-58:

Acronym Commercial Name Chemical Name UH1016 EXTEM (TM) UH4,4′-oxydiphthalic dianhydride TPI (ODPA), and 4,4′-diaminodiphenylsulfone (DDS) XH1015 EXTEM (TM) XH 3,3′ bisphenol-A dianhydride TPI(BPADA), and 4,4′-diaminodiphenyl sulfone (DDS) XH6050 ULTEM (TM) PEI4,4′ bisphenol-A dianhydride (BPADA), and 4,4′-diaminodiphenyl sulfone(DDS) 1000 ULTEM (TM) PEI 4,4′ bisphenol-A dianhydride (BPADA), andmeta-phenylenediamine PEEK VICTREX (TM) Polyether ether ketone PEEK 150Silica Fused SilicaTechniques/Procedures

The following procedures were used in the indicated examples.

Blend Preparation Procedures

Whenever blends were used in these examples, the required resincomponents were dry blended and tumbled. The raw blend was dried at 235°F. (113° C.) for 8 hrs, prior to extrusion. The blend was extruded on a30 mm twin screw, vacuum vent extruder. The extruder was set at 316° C.to 360° C. through 6 zones. The screws ran at 300 rpm and a vacuum waspulled down to 27 in Hg. Pellets were collected after the polymer wascooled through a water bath.

Experimental Procedure

The selected or blend was selected due to the inherent high temperatureand low moisture absorption: Parts were then molded to the dimensionsof:

15 mm×150 mm×1 mm

15 mm×150 mm×2 mm

15 mm×150 mm×3 mm

These parts were first dried in a vacuum oven at 220° C. for 4 hrs. Theparts to be conditioned were then placed in a humidity/temperaturecontrolled chamber as per the following conditions:

60° C./60% RH/120 hr, or

80° C./85% RH/165 hr

These samples, along with a non-conditioned, dry, sample, were placed ina Reflow Machine—Yamato-Seisakusyo NRY-525SMB-5Z, 5-zone convectionchamber. The conveyer speed was set at 300 mm/min and nitrogen waspurged through. The heating profile the Reflow Machine was set through 5zones, at specific temperatures for each part thickness. The parts werepassed through 2 heating conditions, with different peak temperatures.

TABLE 1 Temperature Profile for 260 C. Peak Temp Zone 1 Zone 2 Zone 3Zone 4 Zone 5 Part Thickness 1 mm 170 160 160 182 279 Part Thickness 2mm 170 160 160 187 300 Part Thickness 3 mm 170 160 160 185 310

TABLE 2 Temperature Profile for 270 C. Peak Temp Zone 1 Zone 2 Zone 3Zone 4 Zone 5 Part Thickness 1 mm 170 160 160 182 300 Part Thickness 2mm 170 160 160 185 310 Part Thickness 3 mm 170 160 160 199 318

Examples 1-8 260° C., 1^(st) Pass, Popcorning Evaluation

The purpose of these examples was to evaluate certain compositions inaccordance to the present invention for certain performance properties,namely dimensional stability, popcorning effect (if any).

Compositions illustrating specific embodiments of the present inventionwere prepared in accordance to the Blend Preparation Procedure describedabove. Neat resins were also used. The compositions tested aresummarized in Table 3.

TABLE 3 Ex. Composition Tested Blend Ratio Description/Remarks 1 XH1015Neat Comparative (Neat Resin) 2 UH1006 Neat Comparative (Neat Resin) 3XH1015/PEEK 60/40 Invention 4 XH1015/XH6050 50/50 (Comparative) 5UH1016/PEEK/Silica 33/50/17 (Comparative) 6 UH1016/XH1015 75/25(Comparative) 7 UH1016/XH1015/PEEK 20/50/30 (Comparative) 8UH1016/XH1015/ 17/41/25/17 (Comparative) PEEK/Silica

The above-mentioned compositions/materials were tested in accordance tothe Experimental Procedure described above, with the heating profiledescribed in Table 1, with a single pass through the reflow machine. A“popcorning” effect was noted as a visual defect. This occurred whenresidual moisture, collected after conditioning, converted to steamwithin the part, thereby disrupting the part dimension. The samples wereevaluated. A “Pass” was given to samples that did not exhibit popcorningwhile “Fail” was given to samples that did exhibit a popcorning effect.The results are summarized in Table 4 below:

TABLE 4 Popcorning Results for LED Composition DoE. Peak Temp 260 C.,First Pass Dry (Unconditioned) 60° C./60% RH 80° C./85% RH ExComposition 1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 1 XH1015 PassPass Pass Pass Fail n/a Fail Fail n/a (Comparative) 2 UH1006 Pass PassPass Pass Fail Fail Fail Fail Fail (Comparative) 3 XH1015/ Pass PassPass Pass Pass Pass Pass Pass Pass PEEK (Invention) 4 XH1015/ Pass PassPass Fail Fail n/a Fail Fail Fail XH6050 (Comparative) 5 UH1016/ PassPass Pass Pass Pass Fail Pass Pass Fail PEEK/Silica (Comparative) 6UH1016/ Pass Pass Pass Fail Fail Fail Fail Fail Fail XH1015(Comparative) 7 UH1016/ Pass Pass Pass Pass Fail Fail Fail Fail FailXH1015/ PEEK (Comparative) 8 UH1016/ Pass Pass Pass Pass Pass Pass PassFail Fail XH1015/ PEEK/SilicaDiscussion

These results show that when the parts were dry (unconditioned), notsubject to the heat and moisture conditions, parts having a thickness of1 mm, 2 mm, and 3 mm all passed. However, when the parts were exposed toconditions that included 60° C./60% RH (Relatively Humidity), the onlycomposition that passed at 1 mm, 2 mm, and 3 mm was the composition ofExample 3. All the other materials/compositions failed.

When the parts were exposed to conditions that included 80° C./85% RH,the only composition that passed at 1 mm, 2 mm, and 3 mm was thecompositions of Example 3. All the other materials/compositions failed.

Examples 9-16 260° C., 1^(st) Pass, Warpage Evaluation

The purpose of these examples was to evaluate certain compositions inaccordance to the present invention for certain performance properties,namely dimensional stability, through a warpage criteria.

Preparation Techniques

Compositions illustrating specific embodiments of the present inventionwere prepared in accordance to the Blend Preparation Procedure describedabove. Neat resins were also used. The compositions tested aresummarized in Table 5.

TABLE 5 Ex. Composition Tested Blend Ratio Description/Remarks 9 XH1015Neat Comparative (Neat Resin) 10 UH1006 Neat Comparative (Neat Resin) 11XH1015/PEEK 60/40 Invention 12 XH1015/XH6050 50/50 (Comparative) 13UH1016/PEEK/Silica 33/50/17 (Comparative) 14 UH1016/XH1015 75/25(Comparative) 15 UH1016/XH1015/PEEK 20/50/30 (Comparative) 16UH1016/XH1015/ 17/41/25/17 (Comparative) PEEK/SilicaTesting Techniques

The above-mentioned compositions/materials were tested in accordance tothe Experimental Procedure described above, with the heating profiledescribed in Table 1, with a single pass through the reflow machine.

The part warpage was measured with a micrometer. An acceptable warpagemeasurement is defined as less than 0.3 mm increase at the apex of thepart. Samples that “popcorned” in earlier examples were not measured.

Results:

TABLE 6 260° C. First Pass Dry 60° C./60% RH 80° C./85% RH Ex Composite1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 9 XH1015 0.00 0.00 0.000.01 (Comparative) 10 UH1006 0.00 0.00 0.01 0.01 (Comparative) 11XH1015/ 0.00 0.01 0.03 0.00 0.01 0.03 0.00 0.01 0.02 PEEK (Invention) 12XH1015/ 0.00 0.04 0.05 XH6050 (Comparative) 13 UH1016/ 0.01 0.00 0.050.01 0.00 n/a 0.00 0.01 n/a PEEK/Silica (Comparative) 14 UH1016/ 0.000.00 0.00 XH1015 (Comparative) 15 UH1016/ 0.00 0.01 0.02 0.00 XH1015/PEEK (Comparative) 16 UH1016/ 0.02 0.01 0.00 0.01 0.02 0.02 0.02 XH1015/PEEK/Silica (Comparative)Discussion

As evidenced by Table 6, all of the articles exhibited sufficientwarpage resistance and passed the warpage criteria. None of theComparative Examples performed as well as the compositions of Example11. These results show that any part that did not popcorn has passed thewarpage test for this heating profile. Dry (unconditioned), parts havinga thickness of 1 mm, 2 mm, and 3 mm all passed. Parts conditioned at 60°C./60% RH and 85° C./85% RH also passed.

Examples 17-21 260° C., 1^(st) Pass, XH1015-PEEK, Popcorning Evaluation

Of the compositions evaluated, the XH1015-PEEK sample performed best inthe reflow test. The composition passed the all conditions during thereflow and displayed the greatest dimensional stability.

The P2-PEEK composition was the focus of a second DoE, Table 7, andSilica was added as a potential cost reduction for the blend.

TABLE 7 Example Composition Tested Blend Ratio Description/Remarks 17XH1015/PEEK/Silica 75/15/10 Comparative 18 XH1015/PEEK/Silica 65/15/20Comparative 19 XH1015/PEEK/Silica 55/15/30 Comparative 20XH1015/PEEK/Silica 65/5/30 Comparative 21 XH1015/PEEK/Silica 25/66/9Invention

The above-mentioned compositions/materials were tested in accordance tothe Experimental Procedure described above, with the heating profiledescribed in Table 1, with a single pass through the reflow machine. A“popcorning” effect was noted as a visual defect. This occurred whenresidual moisture, collected after conditioning, converted to steamwithin the part, thereby disrupting the part dimension. The samples wereevaluated. A “Pass” was given to samples that did not exhibit popcorningwhile “Fail” was given to samples that did exhibit a popcorning effect.The results are summarized in Table 8 below:

TABLE 8 260° C. Single pass Dry 60° C./60% RH 80° C./85% RH Ex ComponentRatio 1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 17 XH1015/ 75/15/10Pass Pass Pass Pass Fail Fail Pass Fail Fail PEEK/ Silica 18 XH1015/65/15/20 Pass Pass Pass Pass Fail Fail Pass Fail Fail PEEK/ Silica 19XH1015/ 55/15/30 Pass Pass Pass Pass Fail Fail Fail Fail Fail PEEK/Silica 20 XH1015/ 65/5/30 Pass Pass Pass Pass Fail Fail Fail Fail FailPEEK/ Silica 21 XH1015/ 25/66/9 Pass Pass Pass Pass Pass Pass Pass PassPass PEEK/ Silica

These results show that when the parts were dry (unconditioned), notsubject to the heat and moisture conditions, parts having a thickness of1 mm, 2 mm, and 3 mm all passed. However, when the parts were exposed toconditions that included 60° C./60% RH (Relatively Humidity), the onlycomposition that passed at 1 mm, 2 mm, and 3 mm was the compositions ofExample 21. All the other compositions failed.

When the parts were exposed to conditions that included 80° C./85% RH,the only composition that passed at 1 mm, 2 mm, and 3 mm was thecompositions of Example 21. All the other compositions failed

Examples 22-26 260° C., 1^(st) Pass, XH1015-PEEK, Warpage Evaluation

Of the compositions evaluated, the XH1015-PEEK sample performed best inthe reflow test. The composition passed the all conditions during thereflow and displayed the greatest dimensional stability.

The P2-PEEK composition was focus for a second DoE, and Silica was addedas a potential cost reduction for the blend.

The purpose of these examples, shown in Table 9, was to evaluate certaincompositions in accordance to the present invention for certainperformance properties, namely dimensional stability, through a warpagecriteria.

TABLE 9 Example Composition Tested Blend Ratio Description/Remarks 22XH1015/PEEK/Silica 75/15/10 Comparative 23 XH1015/PEEK/Silica 65/15/20Comparative 24 XH1015/PEEK/Silica 55/15/30 Comparative 25XH1015/PEEK/Silica 65/5/30 Comparative 26 XH1015/PEEK/Silica 25/66/9Invention

The above-mentioned compositions/materials were tested in accordance tothe Experimental Procedure described above, with the heating profiledescribed in Table 1, with a single pass through the reflow machine.

The part warpage was measured with a micrometer. An acceptable warpagemeasurement is defined as less than 0.3 mm increase at the apex of thepart. Samples that “popcorned” in earlier examples were not measured.

Results:

TABLE 10 Dry 60° C./60% RH 80° C./85% RH Ex Component Ratio 1 mm 2 mm 3mm 1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 22 XH1015/ 75/15/10 0.5 1.0 0.3 7.0 n/an/a 6.0 n/a n/a PEEK/ Silica 23 XH1015/ 65/15/20 3.5 2.0 0.3 5.0 n/a n/a14.0 n/a n/a PEEK/ Silica 24 XH1015/ 55/15/30 2.0 1.0 0.3 5.0 n/a n/an/a n/a n/a PEEK/ Silica 25 XH1015/ 65/5/30 1.5 0.5 0.3 7 n/a n/a n/an/a n/a PEEK/ Silica 26 XH1015/ 25/66/9 0.3 0.3 0 1 0.5 0.00 0.5 0.3 0.5PEEK/ Silica

The results in Table 10 show that only Example 26 passed the warpagetest for this heating profile. Every other example had failing parts atevery moisture conditions.

Examples 27-34 260° C., 2^(nd) Pass, Popcorning Evaluation

The purpose of these examples was to evaluate certain compositions inaccordance to the present invention for certain performance properties,namely dimensional stability, popcorning effect (if any). Further,compositions were subjected to a second pass/run was used to furtherevaluate the robustness of the composite, with a second heat-history.

Preparation Procedures

Compositions illustrating specific embodiments of the present inventionwere prepared in accordance to the Blend Preparation Procedure describedabove. Neat resins were also used. The compositions tested aresummarized in Table 11.

TABLE 11 Example Composition Tested Blend Ratio Description/Remarks 27XH1015 Neat Comparative (Neat Resin) 28 UH1006 Neat Comparative (NeatResin) 29 XH1015/PEEK 60/40 Invention 30 XH1015/XH6050 50/50(Comparative) 31 UH1016/PEEK/Silica 33/50/17 (Comparative) 32UH1016/XH1015 75/25 (Comparative) 33 UH1016/XH1015/ 20/50/30(Comparative) PEEK 34 UH1016/XH1015/ 17/41/25/17 (Comparative)PEEK/SilicaTesting Procedures

The above-mentioned compositions/materials were tested in accordance tothe Experimental Procedure described above, with the heating profiledescribed in Table 1, except that the respective composition wassubjected to a second pass through the reflow machine.

A “popcorning” effect was noted as a visual defect. Popcorning occurredwhen residual moisture, collected after conditioning, converted to steamwithin the part, thereby disrupting the part dimension. The samples wereevaluated. A “Pass” was given to samples that did not exhibit popcorningas well as warpage while a “Fail” was given to samples that did exhibita popcorning effect.

Results

The results obtained are summarized in Table 12 below:

TABLE 12 Dry 60° C./60% RH 80° C./85% RH Ex Composition 1 mm 2 mm 3 mm 1mm 2 mm 3 mm 1 mm 2 mm 3 mm 27 XH1015 Pass Pass Pass Pass Fail Fail FailFail Fail 28 UH1006 Pass Pass Pass Pass Fail Fail Fail Fail Fail 29XH1015/PEEK Pass Pass Pass Pass Pass Pass Pass Pass Pass 30XH1015/XH6050 Pass Pass Pass Fail Fail Fail Fail Fail Fail 31 UH1016/Pass Pass Pass Pass Pass Fail Pass Fail Fail PEEK/Silica 32 UH1016/ PassPass Pass Fail Fail Fail Fail Fail Fail XH1015 33 UH1016/ Pass Pass PassPass Fail Fail Fail Fail Fail XH1015/PEEK 34 UH1016/ Pass Pass Pass PassFail Fail Fail Fail Fail XH1015/ PEEK/SilicaDiscussion

These results show that when the parts were dry (unconditioned), notsubject to the heat and moisture conditions, parts having a thickness of1 mm, 2 mm, and 3 mm all passed. However, when the parts were exposed toconditions that included 60° C./60% RH (Relatively Humidity), the onlycomposition that passed at 1 mm, 2 mm, and 3 mm was the compositions ofExample 29. All the other materials/compositions failed.

When the parts were exposed to conditions that included 80° C./85% RH,the only composition that passed at 1 mm, 2 mm, and 3 mm was thecompositions of Example 29. All the other materials/compositions failed.

Examples 35-42 260° C., 2^(nd) Pass, Warpage

The purpose of these examples was to evaluate certain compositions inaccordance to the present invention for certain performance properties,namely dimensional stability, through a warpage criteria.

Preparation Techniques

Compositions illustrating specific embodiments of the present inventionwere prepared in accordance to the Blend Preparation Procedure describedabove. Neat resins were also used. The compositions tested aresummarized in Table 13.

TABLE 13 Example Composition Tested Blend Ratio Description/Remarks 35XH1015 Neat Comparative (Neat Resin) 36 UH1006 Neat Comparative (NeatResin) 37 XH1015/PEEK 60/40 Invention 38 XH1015/XH6050 50/50(Comparative) 39 UH1016/PEEK/Silica 33/50/17 (Comparative) 40UH1016/XH1015 75/25 (Comparative) 41 UH1016/XH1015/ 20/50/30(Comparative) PEEK 42 UH1016/XH1015/ 17/41/25/17 (Comparative)PEEK/SilicaTesting Techniques

The above-mentioned compositions/materials were tested in accordance tothe Experimental Procedure described above, with the heating profiledescribed in Table 1, except that the respective composition wassubjected to a second pass through the reflow machine.

The part warpage was measured with a micrometer. An acceptable warpagemeasurement is defined as less than 0.3 mm increase at the apex of thepart. Samples that “popcorned” in earlier examples were not measured.

Results:

TABLE 14 260° C. Second Pass Dry 60° C./60% RH 80° C./85% RH Ex.Composite 1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 35 XH1015 0.000.03 0.00 36 UH1006 0.00 0.00 0.01 0.00 37 XH1015/PEEK 0.00 0.01 0.010.00 0.01 0.01 0.02 38 XH1015/XH6050 0.01 0.04 39 UH1016/ 0.00 0.00 0.000.00 0.00 PEEK/Silica 40 UH1016/XH1015 0.00 0.00 0.00 41 UH1016/ 0.010.01 0.02 0.01 XH1015/PEEK 42 UH1016/ 0.01 0.01 0.00 0.01 0.02 XH1015/PEEK/Silica

The results represented in Table 14, show that any part that did notpopcorn, passed the warpage test for this heating profile. Dry(unconditioned), parts having a thickness of 1 mm, 2 mm, and 3 mm allpassed. Part conditioned at 60° C./60% RH and 85° C./85% RH, whichpassed the popcorn criteria, also passed the warpage criteria.

Examples 43-50 270° C., 1^(st) Pass, Popcorning Evaluation

The purpose of these examples was to evaluate certain compositions inaccordance to the present invention for certain performance properties,namely dimensional stability, popcorning effect (if any).

Preparation Procedures

Compositions illustrating specific embodiments of the present inventionwere prepared in accordance to the Blend Preparation Procedure describedabove. Neat resins were also used.

The compositions tested are summarized in Table 15.

TABLE 15 Example Composition Tested Blend Ratio Description/Remarks 43XH1015 Neat Comparative (Neat Resin) 44 UH1006 Neat Comparative (NeatResin) 45 XH1015/PEEK 60/40 Invention 46 XH1015/XH6050 50/50(Comparative) 47 UH1016/PEEK/Silica 33/50/17 (Comparative) 48UH1016/XH1015 75/25 (Comparative) 49 UH1016/XH1015/ 20/50/30(Comparative) PEEK 50 UH1016/XH1015/ 17/41/25/17 (Comparative)PEEK/SilicaTesting Procedures

The above-mentioned compositions/materials were tested in accordance tothe except that the respective composition was subjected to a singlepass through the reflow machine.

A “popcorning” effect was noted as a visual defect. This occurred whenresidual moisture, collected after conditioning, converted to steamwithin the part, thereby disrupting the part dimension. The samples wereevaluated. A “Pass” was given to samples that did not exhibit popcorningas well as warpage while a “Fail” was given to samples that did exhibita popcorning and warpage effect. The results are summarized in Table 16below:

TABLE 16 Popcorning Results for LED Composition DoE. Peak Temp 270 C.,First Pass Dry 60° C./60% RH 80° C./85% RH Ex Composition 1 mm 2 mm 3 mm1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 43 XH1015 Pass Pass Fail Fail Fail FailFail Fail Fail 44 UH1006 Pass Pass Pass Fail Fail Fail Fail Fail Fail 45XH1015/PEEK Pass Pass Pass Pass Pass Pass Pass Pass Pass 46 XH1015/ PassPass Fail Fail Fail Fail Fail Fail Fail XH6050 47 UH1016/PEEK/ Pass PassPass Pass Pass Fail Pass Pass Fail Silica 48 UH1016/ Pass Pass Pass FailFail Fail Fail Fail Fail XH1015 49 UH1016/ Pass Pass Pass Fail Fail FailFail Fail Fail XH1015/PEEK 50 UH1016/ Pass Pass Pass Fail Fail Fail FailFail Fail XH1015/PEEK/ SilicaDiscussion

These results show that when the parts were dry (unconditioned), notsubject to the heat and moisture conditions, parts having a thickness of1 mm, 2 mm, and 3 mm, only examples 44, 45, 47, 48, 49, and 50 passed.However, when the parts were exposed to conditions that consisted of 60°C./60% RH (Relatively Humidity), the only composition that passed at 1mm, 2 mm, and 3 mm was the compositions of Example 45. All the othermaterials/compositions failed.

When the parts were exposed to conditions that included 80° C./85% RH,the only composition that passed at 1 mm, 2 mm, and 3 mm was thecompositions of Example 45. All the other materials/compositions failed.

Examples 51-58 270° C., 1^(st) Pass, Warpage Evaluation

The purpose of these examples was to evaluate certain compositions inaccordance to the present invention for certain performance properties,namely dimensional stability, through a warpage criteria.

Preparation Techniques

Compositions illustrating specific embodiments of the present inventionwere prepared in accordance to the Blend Preparation Procedure describedabove. Neat resins were also used. The compositions tested aresummarized in Table 17.

TABLE 17 Example Composition Tested Blend Ratio Description/Remarks 51XH1015 Neat Comparative (Neat Resin) 52 UH1006 Neat Comparative (NeatResin) 53 XH1015/PEEK 60/40 Invention 54 XH1015/XH6050 50/50(Comparative) 55 UH1016/PEEK/Silica 33/50/17 (Comparative) 56UH1016/XH1015 75/25 (Comparative) 57 UH1016/XH1015/ 20/50/30(Comparative) PEEK 58 UH1016/XH1015/ 17/41/25/17 (Comparative)PEEK/SilicaTesting Techniques

The above-mentioned compositions/materials were tested in accordance tothe Experimental Procedure described above, with the heating profiledescribed in Table 2, except that the respective composition wassubjected to a single pass through the reflow machine.

The part warpage was measured with a micrometer. An acceptable warpagemeasurement is defined as less than 0.3 mm increase at the apex of thepart. Samples that “popcorned” in earlier examples were not measured.

Results:

TABLE 18 270° C. First Pass Dry 60° C./60% RH 80° C./85% RH Ex Composite1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 1 mm 2 mm 3 mm 51 XH1015 0.00 52 UH10060.00 0.00 0.01 53 XH1015/PEEK 0.00 0.01 0.02 0.00 0.01 0.03 0.00 0.000.03 54 XH1015/XH6050 0.03 55 UH1016/ 0.00 0.01 0.00 0.00 0.01 0.01PEEK/Silica 56 UH1016/XH1015 0.00 0.00 0.00 57 UH1016/ 0.01 0.00 0.02XH1015/PEEK 58 UH1016/ 0.00 0.01 0.01 XH1015/ PEEK/Silica

The results represented in Table 18 show that any part that did notpopcorn, passed the warpage test for this heating profile. Dry(unconditioned), parts having a thickness of 1 mm, 2 mm, and 3 mm allpassed. Part conditioned at 60° C./60% RH and 85° C./85% RH, whichpassed the popcorn criteria, also passed the warpage criteria.

Example 59

VICTREX™ PEEK 150 was reported to have a moisture absorption ofapproximately 0.5 wt %, based on immersion for 24 hours according toASTM D570.

These results show that PEEK did not metalized well and, as such, wouldbe an unsuitable choice to make for applications that include reflectorsubstrates.

Any element in a claim that does not explicitly state “means for”performing a specified function, or “step for” performing a specificfunction, is not to be interpreted as a “means” or “step” clause asspecified in 35 U.S.C §112, sixth paragraph. In particular, the use of“step of” in the claims herein is not intended to invoke the provisionsof 35 U.S.C §112, sixth paragraph.

What is claimed is:
 1. A moisture resistant composition comprising apolymeric component consisting essentially of: a) 25 weight percent,based on the total weight of the composition, of a polyetherimidecopolymer made from a monomer mixture comprising 3,3′ bisphenol-Adianhydride (BPADA), and 4,4′-diaminodiphenyl sulfone (DDS); and b) 66weight percent, based on the total weight of the composition, ofpolyetheretherketone (PEEK); the moisture resistant composition furthercomprising c) 9 weight percent, based on the total weight of thecomposition, of a silica filler; wherein, in conditions of dryatmosphere/260° C. and 60° C./60% relative humidity, articles havingthicknesses of 2-3 mm, molded from the moisture resistant composition,each exhibit no popcorning and a warpage of less than or equal to 0.5mm.
 2. The moisture resistant composition of claim 1, wherein themonomer mixture further comprises 3-chlorophthalic anhydride.
 3. Themoisture resistant composition of claim 1, wherein a molded partcomprising the moisture resistant composition of claim 1, and having athickness of 3 mm does not exhibit warping in a dry atmosphere at 260°C.
 4. The moisture resistant composition of claim 1, wherein a moldedpart comprising the moisture resistant composition of claim 1, andhaving a thickness of 3 mm does not exhibit warping at 60° C./60%relative humidity.
 5. The moisture resistant composition of claim 1,wherein the polyetherimide copolymer of component a) is made from amonomer mixture consisting of 3,3′ bisphenol-A dianhydride (BPADA), and4,4′-diaminodiphenyl sulfone (DDS).